4-azolyl-4&#39;-oxdiazolyl-stilbenes



United States Patent 3,351,591 4-AZOLYL-4'-0XDIAZOLYL-STILBENES Adolf Emil Sicgrist, Basel, Erwin Maeder, Aesch, Basel- Land, Peter Liechti, Binningen, and Leonardo Guglielmetti, Basel, Switzerland, assignors to Ciba Limited,

Basel, Switzerland, a company of Switzerland No Drawing. Filed Aug. 31, 1965, Ser. No. 484,089 Claims priority, application Switzerland, Sept. 14, 1964, 11,919/64 9 Claims. (Cl. 260-240) ABSTRACT OF THE DISCLOSURE The compounds of this invention are 4-oxazolyl-4'- oxdiazolyl stilbenes which may be represented by the formula ll N wherein X represents O or v in which Q is hydrogen, alkyl, hydroxyalkyl, cyanoalkyl or alkenyl, aralkyl or aryl and A represents naphthalene, tetrahydronaphthalene or a benzene residue attached as indicated by the valence lines and 2, represents a substituted or unsubstituted member of the group phenyl, flpyridyl, 2-furoyl, 2-thienyl, p-naphthyl, fi-styryl and 4- stilbenzyl.

The above described compounds are especially useful as optical brighteners for organic materials.

The present invention provides new, valuable 4-azolyl- 4-oxdia.zolyl-stilbenes of the general formula where A represents a naphthalene, tetrahydronaphthalene or especially benzene residue which is condensed with the azole ring in the manner indicated by the valency lines; W represents a stilbene residue linked in position 4 with the azole ring and in position 4' with the oxdiazole ring; Z represents an aryl or aralkenyl residue or a heterocyclic residue of aromatic nature and X stands for -0- or (in which Q is a hydrogen atom, an alkyl, hydroxyalkyl, cyanoalkyl or alkenyl group or an aralkyl or aryl residue). As aryl residues for Z in the Formula la there are suitable, for example, those of the naphthalene series or especially those of the benzene series, as aralkenyl residues preferably styryl residues whose benzene nucleus may be further substituted, and as heterocyclic residues of aromatic nature there are particularly suitable pyridine, furan and thiophene residues. Among these compounds there are of special value those of the formula 0 l N-N that is to say 4-oxazolyl-4'-oxdiazolyl-stilbenes, where A 3,351,591 Patented Nov. 7, 1967 where R, and R, are identical or different and each represents a hydrogen atom or halogen atom such as fluorine, bromine or especially chlorine, a linear or branched alkyl group containing up to 18 carbon atoms, for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, isoamyl, n-hexyl, n-octyl, Z-ethylhexyl, n-nonyl, n-dodecyl, n-octadecyl or a residue of the formula Hg (5H; and

(31)) CH: CH;

IIgC- CH:-

or a cycloalkyl group containing 5 or 6 cyclic members, especially cyclohexyl, a phenylallryl group, for example benzyl or cumyl, an aryl group, for example phenyl, methylphenyl, chlorophenyl, methoxyphenyl, ethoxyphenyl, isopropoxyphenyl or n-octoxyphenyl, an alkenyl group, a hydroxyalkyl, alkoxyalkyl or halogenalkyl group, a hydroxyl group, an alkoxy group containing up to 18 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, tertiary butoxy, amoxy, ism amoxy, hexoxy, octoxy, nonoxy, or n-octadecoxy group, an aralkoxy group, a phenoxy group, for example a phenoxy or chlorophenoxy group, a nitrile or cyanoalkyl group, for example cyanoethyl, a carboxyl group, a carboxylic acid ester group containing up to 18 carbon atoms, for example a carboxylic acid alkyl, alkoxyalkyl, alkenyl, aryl or aralkyl ester group, a carboxylic acid amide group which may be substituted by alkyl, aralkyl, cycloalkyl or aryl groups, a earboxylic acid hydrazide group, a carboxyalkyl or carbalkoxy-alkyl group containing up to 12 carbon atoms, such as carboxyethyl, carboxyisopropyl or carbomethoxyethyl, a sulphonic acid group, a sulphonic acid ester group containing up to 18 carbon atoms, such as sulphonic acid alkyl ester or aryl ester groups, a sulphonamide group which contains up to 12 carbon atoms and may be substituted by alkyl or aryl groups, an alkylsulphone or arylsulphone group, for example methylsulphone or phenylsulphone, or an amino group which may be substituted by alkyl, hydroxyalkyl or acyl radicals, and R and R together with two vicinal carbon atoms of the benzene ring may form a six-membered alicycle;'R represents a hydrogen atom or a lower alkyl group containing up to 4 carbon atoms, and R, and R are identical or different and each represents a hydrogen atom, a halogen atom, especially chlorine, an alkyl or alkoxy group containing 1 to 8 carbon atoms, a phenyl group, a free or neutralized carboxyl group (-COO cation) or a functionally converted carboxyl group, for example, a carhoxylic acid ester group or a earboxylic acid amide group, a free or neutralized sulphonic acid 3 group (-50 cation), a sulphonic acid ester group or a sulphonamide group.

Especially preferred 4-oxazolyl-4'-oxdiazolyl-stilbenes according to this invention correspond to the Formula 2b 0 Bl Q O Q Q,

, where R and R are identical or different and each represents a hydrogen atom, an alkyl group containing up to 18 carbon atoms, a cyclohexyl group, a phenylalkyl group containing up to 4 carbon atoms in the alkyl group, a phenyl group, an alkylphenyl group containing up to 4 carbon atoms in the alkyl group, an alkoxy group containing up to 12 carbon atoms, a cyanoalkyl group containing up to 4 carbon atoms, a carboxyl group, a carboxylic acid ester group, a carbonamide group, a carbalkoxyalkyl group, or R together with R and the benzene ring represent a tetrahydronaphthalene ring, and R, and R are identical or different and each represents a hydrogen atom, a halogen atom (especially chlorine), an alkyl or alkoxy group containing 1 to 8 carbon atoms, a phenyl group, a carboxyl group, a carboxylic acid ester group containing up to 18 carbon atoms in the ester grouping, a carbonamide group or a nitrile group.

Among these compounds there are specially important for practical uses those in which R, and R each represents a hydrogen atom, R, represents a residue (of the meaning defined in Formula 2b) in position or 6 of the benzoxazole ring of the Formula 2b, and R stands for a substituent in position 4' of the phenyl residue linked with the oxdiazole ring, which likewise has the same meaning as in the Formula 2a.

The new 4-azolyl-4-oxdiazolyl-stilbenes of the general Formula la can be prepared by various methods.

According to one process, for example, an azolylstilbene monocarboxylic acid halide, especially an acid chloride, of the formula (where A, W and X have the above meanings) is reacted with a monoacylhydrazine of the formula Babb-NH (where Z has the above meaning) in the presence of an organic solvent, and the resulting diacylhydrazine of the if necessary after intermediate isolation, is treated with a dehydrating agent, especially a non-sulphonating dehydrating agent, for example thionylchloride.

According to another process for the manufacture of the new 4-azolyl-4'-oxdiazolyl-stilbenes an azolyl-stilbene monocarboxylic acid hydrazine of the formula (where A, W and X have the above meanings) is reacted in the presence of an organic 591W i l? 3 mOnOcaY' 4 boxylic acid halide, especially acid chloride, of the formula (B) O halogen and the resulting diacylhydrazine of the Formula 6-if desired after previous isolation-is treated with a dehydrating agent, especially a non-sulphonating dehydrating agent such as thionylchloride.

The reaction of the acid halides of the Formula 4 or 8 with the carboxylic acid hydran'des of the Formula 5 or 7 to form the acylhydrazine of the Formula 6 can be carried out in the presence of a tertiary nitrogen base, advantageously at a temperature from 50 to 150 C. It is advantageous to use for this purpose a tertiary nitrogen base whose boiling point is not too low, preferably one that does not boil below C., for example N,N- diethylaniline or N,N-dimethylaniline. Particularly good results have been achieved with cyclic tertiary nitrogen bases such as quinoline and above all pyridine bases such as pyridine itself and an alkylpyridine containing lower alkyl groups, such as 2-, 3- and 4-methylpyridine (picolines), ethylpyridines or mixtures of such pyridine bases.

It has proved particularly advantageous to perform the reaction leading to the acylhydrazine of the Formula 6 in a highboiling, inert, little polar organic solvent, for example ortho-dichlorobenzene or trichlorobenzene, in the presence of the stoichiometrically required amount of a pyridine base because the subsequent cyclization leading to the 1,3,4-oxdiazole without intermediate isolation of the acylhydrazine by dropping in slightly more than the stoichiometrically required amount of thionylchloride at a temperature within the range from to 220 C., advantageously at the boiling temperature of the reaction mixture, proceeds quickly and smoothly.

The new 4-azolyl-4'-oxdiazolyl-stilbenes of the Formula 1a are also obtained when an oxdiazolyl-stilbene compound of the formula rine) is reacted with an ortho-amino compound of the formula (where A and X have the above meanings) according to the following scheme of reactions:

o A pJ-W-O C-Z ILA {-4110 compound of the formula (1a) catalyst. Suitable catalysts are, for example, boric acid, boric anhydride, zinc chloride, para-toluenesulphonic acid, also polyphosphoric acids including pyrophosphoric acid. When boric acid is chosen as catalyst, it is advantageous to use it in an amount of 0.5% to 5%, referred to the weight of the reaction mass as a whole. There may be additionally used high-boiling, polar organic solvents, for example dimethylformamide, dichlorobenzene, trichlorobenzene or aliphatic, possibly etherified, hydroxy compounds, for example propyleneglycol, ethyleneglycol monoethyl ether or diethyleneglycol diethyl ether or highboiling esters of phthalic acid, for example phthalic acid dibutyl ester.

It is, however, preferable to carry out the last-mentioned process in two stages: In the first stage, especially the carboxylic acid chloride of the Formula 9 is condensed in an equimolecular proportion with the orthoamino compound of the Formula 10 in the presence of an organic solvent such as toluene, a xylene, chlorobenzene,

dichlorobenzene, trichlorobenzene or nitrobenzene, at a temperature from 100 to 200 C., whereupon the resulting acyl compound of the Formula 11 is converted into the 4-azolyl-4'-oxdiazolyl-stilbene at a temperature ranging from 150 to 350 C., if desired or required in the presence of a catalyst. When the starting material used is a carboxylic acid chloride, it can be prepared immediately before the condensation with the orthoamino compound and without isolation from the corresponding free carboxylic acid and thionylchloride, if desired or required in the presence of a catalyst, such as pyridine, in the solvent in which subsequently the condensation is to be carried out.

The oxdiazolyl-stilbene compounds of the Formula 9 to be used as starting materials in the last-mentioned process can be prepared by known methods, for example according to the following reaction scheme A or B.

T 0-alkyl IIT l-mo

\ hydrolysis Nil-Nib ()ll liar ox. SOC],

As examples of new 4-azolyl-4-oxdiazolyl-stilbenes of the Formula in or 2b that can be manufactured by the processes described above there may be mentioned the following compounds:

The compound of the formula as well as its analogue of the Formula 45 which is substituted by a phenyl group in position 5 of the benzoxazole ring; the compound of the formula acted with quatemating agents e.g. methyliodide, dimethylsulphate, benzylchloride or toluenesulphonic acid alkyl esters at an elevated temperature, if necessary under superatmospheric pressure;

and its analogue of the Formula 31 which is substituted by a methyl group in position of the benzoxazole ring,

(h) one or several halogenoalkyl groups of the stilbene derivative of the Formula 1a are converted into the cor- If desired, the 4-a2olyl-4'-oxdiazolyl-stilbenes of the Formula la obtained by the processes described above may be used in further reactions. Thus, water-soluble derivatives are obtained when (a) the stilbene derivative of the Formula 1a is sulphonated, eg with sulphuric acid monohydrate, chlorosulphonic acid or with sulphuric acid containing sulphur trioxide, if desired at an elevated temperature, and the sulphonic acid group is then converted with an organic or preferably an inorganic base into the corresponding salts;

(b) one or several primary or secondary amino groups of the stilbene derivative of the Formula 1a is converted with sultones, e.g. with propanesultone or butanesultone at an elevated temperature into the corresponding alkyl sulphonic acid derivative;

(c) one or several primary amino groups of the stilbene derivative of the Formula la are converted with aldehyde-bisulphite compounds e.g. with formaldehyde-alkali metal bisulphite, into the corresponding w-methanesulphonic acid derivative;

(d) one or several primary amino groups of the stilbene derivative of the Formula la are reacted with alkylsulphonic or aralkylsulphonic acids, e.g. bromoethanesulphonic acid or benzylchloride-sulphonic acid;

(e) one or several primary or secondary amino groups or hydroxyl groups of the stilbene derivative of the Formula la are linked through s-triazin-Z-yl bridges with phenolsulphonic acids or anilinesulphonic acids;

(f) in one or several hydroxyl groups of the stilbene derivative of the Formula 1a a polyalkylene ether chain which is sufficiently long to ensure solubility in water is introduced by means of an alkylene oxide such as ethylene oxide or propylene oxide or with a polyalkylene ether monohalide;

(g) one or several groups capable of quaternation present in the stilbene derivative of the Formula 1a are re responding quaternary derivative with tertiary bases e.g. pyridine.

The new optical brighteners of the composition defined above display in the dissolved or finely dispersed state a more or less pronounced fluorescence. They may be used for optically brightening a wide variety of organic materials of high or low molecular weight or materials containing organic substances.

As relevant examples the following groups of organic materials suitable for optical brightening may be mentioned, without thereby in any way restricting the possible scope.

I. Synthetic organic materials of high or low molecular weight:

(a) Polymers based on organic compounds containing at least one polymerizable carbon-to-carbon double bond, i.e. their homopolymers and copolymers and products ob tained by after-treating them, such as cross-linked, grafted or decomposition products, polymer dilutions or the like; relevant examples are:

Polymers based on thfi-UflSfiiUl'fitCd carboxylic acids, especially of acryl compounds (e.g. acrylic esters, acrylic acids, acrylonitrile, acrylamides and their derivatives or their methacrylic analogues), of olefinic hydrocarbons (e.g. ethylene, propylene, isobutylene, styrenes, dienes, especially butadiene, isoprene i.e. also rubbers and rubberlike polymers; furthermore so-called ABS polymers), based on vinyl and vinylidene compounds (e.g. vinyl esters, vinylchloride, vinylsulphonic acid, vinyl cthers,

vinyl alcohol, vinylidene chloride, vinylcarbazole), of halogenated hydrocarbons (chloroprene, highly halogenated ethylenes), of unsaturated aldehydes and ketones (e.g. acrolein or the like), of allyl compounds or the like; graft polymerization products (e.g. by grafting vinylic monomers), cross-linked products (e.g. by means of bifunctional or polyfunctional cross-linking agents such as divinylbenzene, polyfunctional allyl compounds or hisacryl compounds), or products accessible by partial decomposition (hydrolysis, depolymerization) or modification of reactive groupings (e.g. esterification, etherification, halogenation, auto-crosslinking).

(b) Other polymers accessible, for example, by ring opening e.g. polyamides of the polycaprolactam type; furthermore formaldehyde polymers or polymers accessible by polyaddition as well as by polycondensation, such as polyethers, polythioethers, polyacetals and thioplasts;

(c) Polycondensation products or precondensates based on bifunctional or polyfunctional compounds containing condensable gro'ups, their homoand co-condensates and products obtained by after-treating them; relevant examples are:

Polyesters, saturated (e.g. polyethylene terephthalate) or unsaturated (e.g. maleic acid-dialcohol polycondensates and their crosses-linked products with polymerizable vinyl monomers), linear or branched (also those based on polyhydric alcohols e.g. alkyd resins).

Polyamides (e.g. hexamethylenediamine adipate), maleinate resins, melamine resins, phenolic resins (novolaks), aniline resins, furan resins, carbamide resins and their precondensates, and similarly constituted products, polycarbonates, silicone resins and others.

(d) Polyadducts such as polyurethanes (if desired cross-linked), epoxy resins.

II. Semisynthetic organic materials e.g. cellulose esters or mixed esters (acetate, propionate, nitrocellulose, cellulose ethers), regenerated cellulose, viscose, cuprammonium cellulose) or products obtained by after-treating them; casein plastics.

III. Natural organic materials of animal or vegetable origin, e.g. based on cellulose or proteins such as wool, cotton, silk, bust, jute, hemp, furs and hairs, leathers, finely dispersed wood masses, natural resins (such as colophony, especially lacquer resins); furthermore rubber, gutta percha, balata and products obtained by aftertreating or modifying them (e.g. by curing, cross-linking or grafting), decomposition products (e.g. by hydrolysis, depolymerization), products accessible by conversion of reactive groups (e.g. by acylation, halogenation, cross-linking or the like).

The organic materials that can be optically brightened may be at any stage of their processing (raw materials, semi-finished products or finished articles) and physical states. They may be in the form of structures of any desired shape, that is to say, for example, they may be predominantly three-dimensional bodies such as blocks, plates, sections, pipes, injection mouldings or components of any desired kind, chips or granulates, formed articles; predominantly two-dimensional bodies such as filaments, fibres, flocks, bristles or wires. The said materials may also be as yet not shaped and be in the most varied homogeneous and inhomogeneous forms of dispersion and physical states, for example in the form of powders, solutions, emulsions, dispersions, latices (e.g. lacquer solutions, polymer dispersions), sols, gels, putties, pastes, waxes, adhesives, pore fillers or the like.

Fibrous materials may, for example, take the form of continuous filaments, staple fibers, flocks, hanks, textile threads, yarns, doubled yarns, fibre fleeces, felts, cottonwool, fiocculated products or of textile fabrics or textile laminates, knitwear, of papers, cardboards, paper pulps or the like.

The compounds to be used according to this invention are of special value for the treatment of textile organic materials, especially woven textile fabrics. If fibreswhich may be staple fibres or continuous filaments, in the form of banks, woven or knitted fabrics, fleeces, fiocculated substrates or laminates--are to be optically brightened by the present process, this is advantageously done in an aqueous medium in which the chosen compound is finely dispersed (suspended or, if desired, dissolved). If desired, there may be added to the treatment liquor a dispersant, for example soaps, polyglycol ethers of fatty alcohols, fatty amines or alkylphenols, cellulose sulphite waste liquor or condensation products of (possibly alkylated) naphthalenesulphonic acids with formaldehyde. It has been found particularly advantageous to work in a neutral, weakly alkaline or acid bath. Likewise, it is advantageous to perform the treatment at a temperature from about 50 to 100 C., for example at the boiling temperature of the bath or in its vicinity (at about C.). The improving treatment according to this invention may also be carried out with solutions in organic solvents.

Furthermore, the new optical brighteners to be used in this invention may be added to, or incorporated with, the materials before or during their shaping. Thus, for example, in the manufacture of films, foils, tapes or mouldings they may be added to the moulding or injection moulding composition or they may be dissolved, dispersed or in any other way finely and homogeneously distributed in the spinning mass before spinning. The optical brighteners may also be added to the starting materials, reaction mixtures or intermediate products used to produce fully synthetic or semi-synthetic organic materials, that is to say before or during the chemical reaction, e.g. a polycondensation (including the precondensates), a polymerization (including the prepolymer) or a polyaddition.

The new optical brighteners can, of course, also be used whenever organic materials of the kind indicated above are combined with inorganic materials in any desired form (typical examples: detergents, white pigments in organic substances).

The new optical brighteners are distinguished by their particularly good heat resistance and fastness to light and to migration.

The amount of the new optical brightener to be used according to this invention, referred to the weight of the material to be optically brightened, may vary within wide limits. Even very small amounts, in some cases for instance as little as 0.001% by weight, may sufiice to produce a distinct and durable effect, though it is also possible to use amounts of up to about 0.5% by weight or more. For most practical purposes an amount ranging from 0.01 to 0.2% by weight will be preferred.

The new compounds, to be used as brightening agents, may also be applied, for example, as follows:

(a) In admixture with dyestuffs or pigments or as additives to dyebaths, or printing, discharge or reserve pastes. Also for after-treating dyeings, prints or discharge prints.

(b) In admixture with so-called carriers," antioxidants, light filters, heat stabilizers, chemical bleaches or as additives to bleaching baths.

(c) In admixture with cross-linking agents, dressings such as starch or synethetic dressings. It may be of advantage to add the products of this invention to the liquors used for producing an anti-crease finish.

(d) In combination with detergents, the detergent and the optical brightener may be added separately to the washing liquor. It is also advantageous to use detergents that as such already contain a share of brightening agent. Suitable detergents are e.g. soaps, salts of sulphonate washing agents e.g. of sulphonated benzimidazoles substituted on the carbon atom 2 by higher alkyl radicals, also salts of monoearboxylic acid esters of 4-sulphophthalic acid with higher fatty alcohols, also salts of fatty alcohol sulphonates, alkylarylsulphonic acids or condensation products of higher fatty acids with aliphatic hydroxysulphonic or aminosulphonic acids. Furthermore, there may be used non-ionic detergents e.g. polyglycol ethers derived from ethylene oxide and higher fatty alcohols, alkylphenols or fatty amines.

(e) In combination with polymeric vehicles (polymers, polycondcnsatcs or polyadducts) in which the brightening agent, if desired in addition to other substances, is incorporated in the dissolved or dispersed form, for ex- 11 ample in the case of coating, impregnating or binding agents (solutions, dispersions, emulsions) for textile materials, fleeces, papers or leathers.

(f) As additives to a wide variety of industrial products to improve their presentation or to obviate disadvantages in their use, for example as additives to glues, adhesives, paints or the like.

The compounds of the above formulae can be used as scintillators for various photographic purposes, such as electrophotographic reproduction or for supersensitizrng.

If the brightening operation is to be combined with other treating or improving operations, the combined treatment is advantageously performed with the use of a suitable stable preparation which contains in addition to optically brightening compounds of the above general formula also dispersants, detergents, carriers, dyestuffs, pigments or dressing agents.

When treating a number of fibrous substrates, e.g. polyester fibers, with the brighteners of this invention it is advantageous to impregnate these fibres with an aqueous dispersion of the brightener at a temperature below 75 C., e.g. at room temperature, and then to subject them to a dry heat treatment at a temperature above 100 C. In general, it is of advantage first to dry the impregnated fibrous material at a moderately raised temperature, e.g. at a temperature from at least 60 C. to about 100 C. The heat treatment of the dry material is then advantageously' carried out at 120 to 225 C., for example by heating in a drying chamber, by ironing within the indicated temperature range or by treatment with dry, superheated steam. If desired, the drying and the dry heat treatment may follow immediately upon each other or they may be performed in a single stage.

Example 1 A mixture of 9.18 g. of the diacylhydrazine of the formula 0 o crr=orr o \NHH The crude suction filter cake is stirred for 60 minutes in 2 litres of N-aqueous triethanolamine solution and the undissolved matter is filtered ofi. The solution is acidified with concentrated hydrochloric acid, the resulting precipitate is suctioned off, washed until neutral and dried, to yield about 231 g. of the monocarboxylic acid of the formula s a C CH=CH C HO 0 clHl C( 0 CI I is obtained in a yield of about 97% of the theoretical. Colourless crystals from tetrachloroethylene, melding at 134 to 136 C.

C H 0 Cl: mol. weight, 314.77. Calculated: C, 68.68%; H, 4.80%, Cl 11.26%. Found: C, 68.28%; H, 4.83%; Cl, 11.54%.

A mixture of 31.4 g. of the acid chloride of the Formula 19, 11.0 g. of 1-hydroxy-2-aminobenzene and 500 ml. of dry ortho-dichlorobenzene is stirred for 15 hours at 136 C.; the dark solution is mixed with 1 g. of boric acid, heated to 180 C. while distilling oil 300 ml. of ortho-dichlorobenzene and 2 ml. of water, and further stirred at this temperature for 2 hours. After cooling, suctioning, washing with methanol and drying there are obtained about 24.2 g. of the compound of the formula in the form of a light-brown powder. After three recrystallizations from ortho-dichlorobenzene with the aid of bleaching earth there are obtained small, light-yellow, shiny needles melting at 287 to 288 C.

c,,rr,,o,rr,= mol. weight, 441.47. Calculated: C, 81.22%; H, 4.48%; N, 8.12%. Found: C, 81.03%; H, 4.73%; N, 8.17%.

The diacylhydrazine of the Formula 17 used as starting material can be prepared in the following manner:

A solution of 324 g. of stilbene-4,4-dicarboxylic acid diethyl ester in 1 litre of ethanol and 4 litres of dioxane is mixed at C. with 100 ml. of 10 n sodium hydroxide solution. After stirring for 1 hour at 40 C. the resulting thick, cream-coloured paste is cooled to room temperature (about 20 C.), suctioned, washed with dioxane and thoroughly expressed. The moist suction filter cake is stirred for 2 hours in 10 litres of hydrochloric acid of 5% strength, suctioned off and washed neutral with water.

in the form of a light-brown powder melting at 210 to 220 C. Recrystallization from tetrachloroethylene with the aid of bleaching earth furnishes a yellow, crystalline powder melting at 227 to 229 C.

C d-1 0 19: mol. .weight, 369.40. Calculated: C, 78.03%; H, 5.18%; N, 3.79%. Found: C, 78.33%; H, 5.27%;N, 3.75%.

39.6 grams of the ethyl ester 'of the Formula 20 in 300 ml. of dioxane are saponified with 20 ml. of 10 n-sodium hydroxide solution for 4% hours at to C. After addition of ml. of methanol the batch is cooled to room temperature, suctioned and washed with methanol. The moist filter cake is taken up in 1 litre of dimethylformamide, mixed at 100 C. with 40 ml. of concentrated hydrochloric acid, cooled, suctioned, washed 13 14 and dried, to yield about 32.2 g. of the compound of C H mNCl: mol. weight, 359.81. Calculated: C, the formula 73.44%; H, 3.92%; N, 3.89%. Found: C, 73.42%; H,

4.04%; N, 3.86%. (2 A mixture of 7.2 g. of the acid chloride of the For- O 5 mula 22, 2.72 g. of benzoic acid monohydrazide and 100 ml. of pyridine is stirred first while being cooled with ice, then at room temperature and finally for 5 on hours at 90 to 95 C. After cooling, the reaction mixture is poured into 1500 ml. of water, suctioned, washed in the form of a light-yellow powder melting at 318 m with cold and then with hot water and dried, to yield about Sublimation in a high vacuum at funk 8.4 g. of the diacylhydrazme of the Formula 17 in the ishes light yellow crystals f identical melting point form of an almost colourless powder which is used for c rr o m mol. weight, 341.35. Calculated: c, the ring closure withoutpurification- 77.40%; H. 4.43%; N, 4.10%. Found: C, 77.30%; H, The following benzoxazolyl-oxdiazolyl-stilbene com- 4 0% 443% pounds can be prepared in a similar manner:

Occasionally the acid is obtained in a form melting Pale yellow, shiny flakes from ortho-dichlorobenzene, at 349 to 350 C. melting at 305 to 306 C.

The 4-[benzoxazolyl-(2")]-stilbene-4'-carboxylic acid C H, O,N mol. weight, 517.59. Calculated: C, of the Formula 21 is converted in known manner by 30 78.89%; H, 4.34%; N, 9.55%. Found: C, 78.54%; H,

boiling in excess thionylchloride in the presence of a 4.39%;N,9.55%.

C In

catalytic amount of pyridine into the acid chloride of the formula Light greenish yellow, fine needles from ortho-dichloro- O benzene, melting at 290 to 291 C. i c--c =c 0 c m-@ 51 mol. weight, 497.57. Calculated: c, Cl 79.65%; H, 5.47%; N, 8.45%. Found: c, 79.50%; H,

Light-yellow felted needles from ortho-dichlorobenzene, 05 melting at 296 to 297 C. which is obtained in a yield of about 87% of the theoc n om z mol. weight 455.49. Calculated: C, retical. On recrystallization from ortho-dichlorobenzene it forms yellow crystals melting at 266 to 268 C. 4.73%; N, 9.17%.

79.10%; H, 4.65%; N, 9.23%. Found: C, 79.13%; H,

16 dry dichlorobenzene, 200 ml. of thionylchloride and 0.5 ml. of pyridine are added and the mixture is stirred for 3 hours at 90 to 100 C., after which the evolution of hydrochloric acid ceases and a dark solution has formed. The excess thionylchloride is completely evaporated under Fine, yellow needles from ortho-dichlorobenzene, melting at 322 to 323 C.

c ,H,,o,N,c1= mol. weight, 475.94. Calculated: C, 73.19%; H, 3.81%; N, 8.83%. Found: C, 73.43%; H, 3.70%; N, 8.88%.

\ /C- CH=CH E E COOCH: O

vacuum. The residue is cooled to room temperature and 41.1 g. of l amino 2 hydroxy 5 methylbenzene are added. The batch is heated within one hour to the reflux temperature, during which at about 110 C. evolution of hydrochloric acid sets in. When hydrochloric acid is no Light-yellow fine needles from ortho-dichlorobenzene, melting at 317.5 to 318.5" C.

C H 0 N mol. weight, 499.50. Calculated: C, 74.54%; H, 4.24%; N, 8.41%. Found: C, 74.41%; H, 4.29%; N, 8.46%.

Light-yellow flakes from ortho-dichlorobenzene, melting longer being liberated, 2 g. of boric anhydride are added at 300? C. and the temperature is raised to such a value that within C H O N mol. weight, 527.55. Calculated: C, 2 hours the bulk of the solvent passes over together with 75.13%; H, 4.78%; N, 7.97%. Found: C, 74.98%; H, the liberated water. A dark, slightly turbid melt is ob- 4.84%; N, 7.66%. tained which is stirred on for 30 minutes at 230 to 235" Example 2 'I'lzg cllfark meltdis the; mixed droplwisf with 330 ml. of

ime y ormami e, w ereu on a ar solution '5 ob- P 0f f f Y Y ")l' tained. The finely crystalline precipitate is suction ed olf Y acld hydfallde of the formula at room temperature, rinsed with a small amount of dimethylformamide and dried, to yield about 100 g. of a (26) N yellow powder melting at 280 to 284 C.

c-Cfl=CH-C Crystallization from chlorobenzene with the aid of bleaching earth furnishes the compound of the formula 0 23) are suspended in 90 parts by volume of dry dichlorobenzene and 5.4 parts of 4oct0xybenzoylchloride are added.

Then 4 parts by volume of anhydrous pyridine are added -C a l and the whole is raised within 1 hour to the reflux temperature, whereupon a turbid solution forms. In the 0 course of 15 minutes 6 parts by volume of thionylchloride are dropped in at a rate such that the reflux temperatnre of the reaction mixture remains above 168 C. The in the form of light-yellow greenish tinsel melting at batch is stirred on for 10 minutes and then allowed to 282 to 283 C.

cool to room temperature. The precipitate is suctioned C H NO mol. weight, 383.43. Calculated: C, off and rinsed with toluene and alcohol. The residue is 78.31%; H, 5.52%; N, 3.65%. Found: C, 78.28%; H, disolved in boiling xylene, mixed with bleaching earth, 5.50%; N, 3.59%.

filtered clear, concentrated and allowed to cool. After 91.9 grams of 4 [5" methyl benzoxazolyl (2")1- suctioning, washing with methanol and drying there are stilbene 4' carboxylic acid ethyl ester of the Formula obtained about 6.4 parts of the compound of the formula 28 in 1500 ml. of ethyleneglycol monomethyl ether are C CH=CH C C WMM. 1l ll raised to the boil, whereupon a clear solution forms; 150 -ml. of hydrazine hydrate are run in and the whole is refluxed for 20 hours with vigorous stirring, to form a thick, yellow suspension, which is suctioned at room temperature and washed with a small amount of ethyleneglycol monomethyl ether and then with alcohol until the washings run neutral. On drying, there are obtained about 81 in the form of a light-yellow finely crystalline powder melting at 293 to 295 C.

C H O N mol weight, 583.70. Calculated: C, 78.19%; H, 6.40%; N, 7.20%. Found: C, 78.29%; H, 6.55%; N, 7.12%.

The 4 [5" methyl benzoxazolyl (2")] stilbene- 4-carboxylic acid hydrazide of the Formula 26 used as starting material can be prepared in the following manner: g. of the hydrazide of the Formula 26 as a yellowish 98.8 grams of 4 carboxystilbene 4' carboxylic acid powder which can be used for the further condensation ethyl ester of the Formula 18 are suspended in 600 ml. of without previous purification,

- 17 18 The following benzoxazolyl oxdiazolyl stilbene com- Orange-yellow powder from ortho-dichlorobenzene, meltpounds can be prepared in a similar manner: ing at 319 to 321 C.

U c--crr=cH--E:o--cm Pale-yellow, fine needles from ortho-dichlorobenzene, C H N,0,: mol. weight, 480.50. Calculated: C, melting at 308 to 310 C. 77.48%; H, 4.21%; N, 11.66%. Found: C, 77.32%; H,

c,,H,,N,0,: mol. weight, 469.52. Calculated: C, 4.32%;N, 11.75%.

(3 m g C W=CH 79.30%; H, 4.94%; N, 8.95%. Found: C, 79.10%; H, Yellow, crystalline powder from chlorobenzene, melting 4.96%; N, 8.84%. at 258 to 259 C.

( H. N\ 'CH C C Light-yellow flakes from ortho-dichlorobenzene, me1t- C l-1 N 0 mol. weight, 483.54. Calculated: C, ing at 288 to 290 C. 79.48%; H, 5.21%; N, 8.69%. Found: C, 79.20%; H,

0 11 0 19 mol. weight, 455.49. Calculated: C, 5.32%; N, 8.59%.

79.10%; H, 4.65%; N, 9.23%. Found: C, 79.25%; H, Light-yellow, crystalline powder from dimethylform- 4.67%; N, 9.13%. amide, melting at 247 to 248 C.

Pale-yellow, felted, small needles from orth0-dichloroben- C H N O z mol. weight, 497.57. Calculated: C, zene, melting at 323 to 325 C. 79.65%; H, 5.47%; N, 8.45%. Found: C, 79.37%; H,

C l-1 N 0 mol. weight, 531.58. Calculated: C, 5.36%; N, 8.30%.

81.33%; H, 4.74%; N, 7.91%. Found: C, 81.31%; H, Light-yellow, crystalline nowder from 'chlorobenzene, 4.60%; N, 8.20%. melting at 285' C.

C l-1 N 0 mol. weight, 541.58. Calculated: C, 75.40%; H, 5.03%; N, 7.76%. Found: C, 75.16%; H, 5.03%; N, 7.78%.

Small, brilliant yellow needles from ortho-dichlorobenzene, melting at 341 to 343 C.

C H O N S: mol. weight, 537.64. Calculated: C,

Pale-yellow, felted, small needles from ortho-dichlorobenzene, melting at 340 C.

C H N O mol. weight, 557.62. Calculated: C, 81.84%; H, 4.88%; N, 7.53%. Found: C, 81.74%; H, 5.12%; N, 7.71%.

75.96%; H, 4.31%; N, 7.82%. Found: C, 76.15%; H, 4.50%; N, 7.83%.

Light-yellow, small needles from ortho-dichlorobenzene, melting at 300 C.

C H O N -Calcula1ed: C, H, N,

Pale-yellow, crystalline powder from ortho-dichlorobenzene, melting at 278 to 280 C.

8.09%; S, 6.17%. Found: C, 69.31%; H, 4.09%; N, 7.96%; S, 6.23%.

C d-1 N0 2 mol. weight, 456.48. Calculated: C, 76.30%; H, 4.42%; N, 12.27%. Found: C, 76.00%; H, 4.44%; N, 12.20%.

Yellow, crystalline powder from dimethylformamide, melting at 278 to 280 C.

C J-I O N mol. weight, 505.55. Calculated: C,

Small, yellow needles from ortho-dichlorobenzene, melting at 281 to 283 C.

80.77%; H, 4.59%; N, 8.31%. Found: 80.52%; H, 4.66%; N, 8.25%.

C l'l O N mol. weight, 445.46. Calculated: C, 75.49%; H, 4.30%; N, 9.43%. Found: C, 75.16%; H, 4.35%; N, 9.50%.

melting at 295 to 297 C.

C,,H,,0,N,: mol. weight, 481.53. Calculated: C,

- 21 79.81%; H, 4.81%; N, 8.73%. Found: C, 79.72%; H, 4.80%; N, 8.85%.

CHg-ll Example 3 A mixture of 9.5 g. of 4-[5"-tertiary butyl-benzoxazolyl-(2")]-stilbene-4'-carboxylic acid of the formula.

100 ml. of dichlorobenzene, 20 ml. of thionylchloride and 3 drops of pyridine is heated for 4 hours at 90 to 95 C.; hydrochloric acid escapes and a clear solution forms. The excess thionylchloride is then completely evaporated under vacuum. The batch is cooled to room temperature and the pale-yellow suspension of the acid chloride is mixed with 5.8 g. of diphenyM-carboxylic acid hydrazide and 20 ml. of dry pyridine. The whole is stirred for 2 hours at 100 to 1l0 C. and then heated to reflux. Between 160 and 170 C. ml. of thionylchloride are dropped within minutes into the grey-biege suspension, whereupon a dark solution is obtained which is stirred on for 15 minutes at the same temperature, then cooled to room temperature and the condensation product is precipitated with alcohol. Crystallization from chlorobenzene-l-isopropanol with the aid of bleaching earth furnishes 6.5 g. of the compound of the formula 20, to yield 16 g. of 4-[5"-tertiary butyl-benzoxamlyl- (2")l-stilbene-4-carboxylic acid ethyl ester of the formula N o c--on=orr-cooomom as a light-yellow, crystalline powder melting at 172 to 173 C. Crystallization from toluene+cyclohexane with addition of bleaching earth furnishes yellowish time melting at 177 to 178 C. I

C H O N: mol. weight, 425.50. Calculated: C, 79.03%; H, 6.40%; N, 3.29%. Found: C, 78.83%; H. 6.60%; N, 3.52%.

A mixture of 60 g. of ethyl ester of the Formula and 1200 ml. of ethyleneglycol monomethyl ether is heated to refluxing, whereby a thin, yellow suspension is obtained. Within 15 minutes a solution of 11 g. of caustic soda in 100 ml. of water is dropped in, and a thick suspension forms which is refluxed for one hour, cooled to room temperature, suctioned, washed with methanol and dried. The powdered sodium salt is then suspended in 1 litre of dimethylformamide and 25 ml. of formic-acid are added, whereupon a clear solution is obtained which is poured into 5 litres of cold water; the floccular precipitate is suctioned off and the residue is washed with water (1 =QCH=CHQEQEQQ CHg- 15.7 grams of stilbene-4,4'-dicarboxylic acid ethyl ester chloride of the Formula 19 are condensed with 6.1 g. of 3-amino-4-hydroxy-tertiary butylbenzene as described for the manufacture of the compound of the Formula until the washings run neutral to Congo red. After drying there are obtained about 41 g. of the carboxylic acid of the Formula 43 melting at 348 to 349 C. which is used for the following condensation without previous purification.

The following benzoxazolyl-oxdiazolyl-stilbene compounds can be prepared in a similar manner:

Pale yellow, small needles from toluene, melting at 293 to 294 C.

C ,,H O N mol. weight, 527.60. Calculated C,

77.40%; H, 5.54%; N, 7.97%. Found: C, 77.63%; H, 5.52%; N, 7.88%.

(48) on, CHI-J) Yellow, crystalline powder from toluene-l-isopropanol, melting at 280 to 282 C.

C H O N mol. weight, 553.67. Calculated: C, 80.26%; H, 6.37%; N, 7.59%. Found: C, 79.83%; H, 6.33%; N, 7.34%.

Example 4 A mixture of 9.5 g. of 4-[5"-phenyl-benzoxazolyl- (2")]-stilbene-4-carboxylic acid of the formula The 4 [5"-phenyl-benzoxazolyl-(2")]-stilbene-4'-car- 24 in the form of small, yellow needles melting at 320 to 322 C.

C H O N mol. weight, 573.66. Calculated: C, 81.65%; H, 5.45%; N, 7.33%. Found: C, 81.45%; H,

boxylic acid of the Formula 49 used as starting material can be prepared in the following manner:

125.9 grams of stilbene-4,4-dicarboxylic acid ethyl ether chloride of the Formula 19 are condensed with 74.1 g.

of 3-amino-4-hydroxydiphenyl as described for the manufacture of the compound of the Formula 20, to yield 125 m1. of ortho-dichlorobenzene, 20 ml. of thionylchloride and 3 drops of pyridine is heated within 4 hours at to C., during which hydrochloric acid escapes and a clear solution forms. The excess thionylehloride is completely evaporated under vacuum, the residue cooled to room temperature and the faintly yellow suspension of the acid chloride is mixed with 4.4 g. of 4-tertiary butylbenzhydrazide and 20 ml. of dry pyridine. The batch is stirred for 2 hours at to C. and then heated to the reflux temperature, whereby a very thin suspension is obtained. In the course of 15 minutes 10 ml. of thionylchloride are then dropped in at a rate such that the boiling temperature does not drop below 160 C. The batch is stirred on for 15 minutes at the reflux temperature, then allowed to cool and the reaction product is precipitated with methanol. Crystallization from xylene with the aid of bleaching earth furnishes 6.5 g. of the compound of the formula g. of 4-[5"-phenyl-benzoxazolyl-(2")]-stilbene-4- carboxylic acid ethyl ester of the formula 45 c n ons: mol. weight, 445.49. Calculated: c,

80.88%; H, 5.20%; N, 3.14%. Found: C, 80.62%; H, 5.10%; N, 3.32%.

20 grams of ethyl ester of the Formula 51 are saponified in 500 ml. of ethyleneglycol monomethyl ether with 5.5 g. of caustic soda in 50 ml. of water as described for the ethyl ester of the Formula 45. The resulting free carboxylic acid (17.0 g. of a light-yellow powder melting at 346 to 347 C.) of the Formula 49 is used in the following condensation without first having been purified.

The following benzoxazolyl-oxdiazolyl-stilbene compound is obtained in a similar manner:

Yellowish flakes from ortho-dichlorobenzcne, melting at 276 to 279 C.

C H O N mol. weight, 517.59. Calculated: C, 81.22%; H, 4.48%; N, 8.12%. Found: C. 80.95%; H 4.56%; N, 8.15%.

Example 5 A mixture of 9.5 g. of 4-[6"-phenylbenzoxazolyl- (2")]-sti1bene-4'-carboxylic acid of the formula 150 ml. of orthodichlorobenzene, 20 ml. of thionylchloride and 3 drops of pyridine is heated for 4 hours at to C., during which hydrochloric acid escapes and a clear solution is obtained. The excess thionylchloride is then completely evaporated under vacuum. The residue is cooled to room temperature and the suspension of the acid chloride is mixed with 4.4 g. of 4-tertiary butylbenzhydrazide and 20 ml. of dry pyridine, heated with stirring for 2 hours at 100 to C. and further heated in the form of a light-yellow, crystalline powder (from ortho-dichlorobenzene), melting at 213 to 216 C.

C H 0 N: mol. weight, 445.49. Calculated: C, 80.88%; H, 5.20%; N, 3.14%. Found: C, 80.94%; H, 5.04%; N, 3.34%.

12.3 grams of the ethyl ester of the Formula 55 are saponified in 310 ml. of ethyleneglycol monomethyl ether with 3.4 g. of caustic soda in 30 ml. of water as described for the ethyl ester of the Formula 45, to yield 10.5 g. of the free carboxylic acid of the Formula 53 as a faintly yellow powder melting at 348 to 350 C. which is used for 20 the following condensation without first having been purified.

Example 6 A mixture of 6.6 g. of the carboxylic acid chloride of to reflux. Within 15 minutes 10 ml. of thionylchloride 25 the formula are dropped in at a rate such that the refiux temperature does not drop below C. The batch is refluxed for another 15 minutes, cooled to room temperature, and the precipitate is suctioned off and rinsed with methanol. On crystallization from dichlorobenzene with the aid of bleaching earth, followed by crystallization from dimethylformamide, there are obtained 7.8 g. of the compound of the formula in the form of brilliant yellow, small needles melting at 293 to 295 C.

C H O N mol. weight, 573.66. Calculated: C, 81.65%; H, 5.45%; N, 7.33%. Found: C, 81.62%; H, 5.55%; N, 7.46%.

The 4-[6"-phenylbenzoxazolyl (2")] stilbene-4-car boxylic acid of the Formula 53 used as starting material can be prepared thus:

63 grams of stilbene-4,4-dicarboxylic acid ethyl ester 55 chloride of the Formula 19 are condensed with 37.4 g. of 4-amino-3-hydroxydiphenyl as described for the com- /N 0 C 11 Q tQ pound of the Formula 20, to yield 61.8 g. of 4-[6-phenylbenzoxazolyl-(2")]-stilbene-4'-carboxylic acid ethyl ester of the formula 3.0 g. of 2-amino-4-benzylphenol and 20 ml. of anhydrous dichlorobenzene is heated to reflux, during which hydrochloric gas escapes. When the evolution of hydrochloric acid has stopped, 15 ml. of diethyleneglycol dibutyl ether and 300 mg. of boric anhydride are added to the thick, yellow suspension; the dichlorobenzene is distilled off under nitrogen drop by drop until a tem- CIT; 43-011: .5

in the form of lemon-coloured flakes melting at 281 to 282 C.

c H O N z mo]. weight, 587.69. Calculated: C,

methyl ether are refluxed, whereupon a clear solution is obtained. Within minutes a solution of g. of caustic soda in 200 ml. of water are dropped in, whereupon a thick, yellowish suspension is obtained which is refluxed for another hour and then allowed to cool to room temperature and suctioned. The residue is washed with methyloellosolve and chloroform and dried, to yield 160 g. of the sodium salt of the formula CHPiQEQEQQhCH-Q-g-QM ester chloride of the Formula 19 in 3 litres of dry orthodichlorobenzene is mixed with 160 ml. of anhydrous pyridine and stirred for 2 hours at to 0., whereby a thinly liquid, light-beige suspension is formed which is heated to reflux, whereupon a dark solution is obtained. Within 45 minutes ml. of thionylchloride are dropped in at a rate such that the reflux temperature always remains above C. The batch is stirred for another 15 minutes at the reflux temperature, the bulk of the solvent is evaporated under atmospheric pressure and alcohol is added. The whole is suctioned at room temperature,

in the form of a yellow powder which is suspended in 2 litres of chlorobenzene at 80 C. Within 10 minutes 100 ml. of thionylchloride are run in, whereupon a turbid solution is obtained which is stirred for another 10 minutes.

0 The precipitated sodium chloride is suctioned off and the clear filtrate evaporated to dryness under vacuum, to yield 144 g. of the acid chloride of the formula in the form of a yellow powder which melts clearly at 241 to 245 C.

The following benzoxazolyl-oxdiazolyl compounds can be prepared in a similar manner:

4, N o c fil rinsed with alcohol and after drying there are obtained 277 g. of a brown-beige coloured powder melting at 187 to 191 C. Crystallization from tetrachloroethylene with the aid of bleaching earth furnishes 240 g. of the 0xdiazolyl-stilbene compound of the formula (59) CHI Yellow, crystalline powder from toluene, melting at 252 to 253 C.

c n om z mol. weight, 615.74. Calculated: C,

O CHr-iQF EQCH=CHCO O CHaCHI in the form of a light-beige coloured powder.

81.92%; H, 6.06%; N, 6.82%. Found: C, 81.92%; H,

C H O N mol. weight, 452.53. Calculated: C, 60 6.04%;N, 6.72%.

76.97%; H, 6.24%; N, 6.19%. Found: C, 76.67%; H, 6.20%; N, 6.10%.

202.7 grams of oxdiazolyl-stilbene-carboxylic acid ester N on or; CH 0 CH1 C CW g age...

\ Pi 41H:

Yellow, crystalline powder from toluene, melting at 273 275 C.

C H O N,: mol. weight, 539.65. Calculated: C, 80.12%; H, 6.16%; N, 7.79%. Found: C, 79.72%, H,

of the Formula 58 in 2 litres of ethyleneglycol mono- 75 6.11%; N, 7.77%.

Yellow beige coloured crystalline powder from ethyl acetate, melting at 188 to 190 C.

NCCHICH C 1-l O N -Calculated: C, 81.16%; H, 7.72%; N, 6.31%. Found: C, 80.95%; H, 7.63%; N, 6.46%.

Light-yellow, crystalline powder from xylene, melting at 253 to 255 C.

C31H33O3N3I mol. weight, 551.66. Calculated: C,

CHIOO CCHaCH 80.55%; H, 6.03%; N, 7.62%. Found: C, 80.30%, H, 6.09%; N, 7.47%.

Yellow, crystalline powder from xylene, melting at 290 50 to 292 C.

c m-9,14,: mol. weight, 579.71. Calculated: C,

EQ-igm 80.86%; H, 7.27%; N, 6.74%. Found: C, 81.00%; H, 7.25%; N, 6.69%.

Light-beige, small needles from xylene ,melting at 313 to 315 C.

c,,H,,0,N,= mol. weight, 548.62. Calculated: C,

78.81%; H, 5.14%; N, 10.21%. Found: C, 78.62%; H, 5.45%; N, 10.18%.

Light-yellow, small needles from toluene, melting at 272 to 274 C.

C I-1 0,1 1 mol. weight, 583.66. Calculated: C, 76.14%; H, 5.70%; N, 7.20%. Found: C, 76.06%; H, 5.68%; N, 7.28%.

80.80%; H, 6.43%; N, 7.25%. Found: C, 80.58%; H, 00 Light-yellow flakes from chlorobenzene, melting at 323 Yellowish, crystalline powder from cyclohexane, melting at 245 to 246 C.

to 325 C.

C H O N mol. weight, 555.61. Calculated: C, 75.66%; H, 5.26%; N, 7.56%. Found: C, 75.42%; H,

C H O N mol. weight, 623.80. Calculated: C, 5.31%;N, 7.46%.

CHICH3OOC Brilliant yellow, crystalline powder from xylene, melting at 298 to 300 C.

C i-1 0 1 1 mol. weight, 569.63. Calculated: C, with 300 ml. of thionylchloride and a few drops of pyri- 75.90%; H, 5.49%; N, 7.38%. Found: C, 75.97%; H, 5.52%; N, 7.47%.

Fine, greenish yellow needles from toluene, melting at 232 to 234 C.

C H O N mol. weight, 585.63. Calculated: C, 73.83%; H, 5.34%; N, 7.18%. Found: C, 73.33%; H, 5.33%; N, 7.05%.

dine and stirred for 12 hours at 90 to 95 C., whereupon a yellow-greenish suspension is obtained which is heated to the reflux temperature in the course of one hour, during which the excess thionylchloride passes over, but no solution is obtained. The batch is suctioned at room tem- O O o /C CH=CH C\C1 Example 7 and the residue washed first with a small amount of ethylin the form of small, yellow needles which melt at 350 C. with decomposition.

Example 8 A suspension of 7.55 g. of the acid chloride of the Formula 73 in ml. of anhydrous chlorobenzene is mixed with 5 g. of l-oetadecanol and 2 ml. of anhydrous 45 pyridine and refluxed for 6 hours, then allowed to cool,

the pale-yellow precipitate is suctioned oil and the residue is washed with acetone. 'lXvo recrystallizations from ortho-dichlorobenzene with the aid of bleaching earth furnish 6.1 g. of the compound of the formula N (l G Q; W on eneglycol monomethyl ether and then with water until the washings run neutral to Congo red. After drying there are obtained 125 g. of the carboxylic acid of the formula in the form of a light-yellow powder melting at 268 to 270 C.

C H 0 N mol. weight, 737.94. Calculated: C, 78.12%; H, 7.51%; N, 5.69%. Found: C, 77.81%;

. 33 34 The following benzoxazolyl-oxdiazolyl-stilbene compounds can be prepared in a similar manner:

CQOH31OQN3: mol. weight, 617.67. Calculated: C, 77.78%; H, 5.06%; N, 6.80%. Found: 77.59%; H, 4.99; N, 7.00%.

Pale-yellow, crystalline powder from chlorobenzene, melting at 265 to 266 C.

C H O N Calttulated: C, H, N, 6.67%. Found: C, 72.23%; H, 5.58%; N, 6.84%.

Light-beige, crystalline powder from trichlorobenzene, which does not melt below 350 C.

C CH==CH C C OCH:CH=CH: 0/ Q Q,

C H O N mol. weight, 1025.09. Calculated: C, Light-yellow, felted, small needles from ortho-dichloro- 40 74.99%; H, 4.33%; N, 8.20%. Found: C, 74.54; H, benzene, melting at 320 C. 4.19; N, 8.32%.

C H O N mol. weight, 525.54. Calculated: C, 75.4l%; H, 4.41%; N, 8.00%. Found: C, 75.62%; H, 4.43%; N, 7.89%.

Example 9 A mixture of 5.03 g. of the acid chloride of the Formula 73, 200 ml. of anhydrous dichlorobenzene and 10 ml.

O 0 EQE OCH Small, yellow, felted needles from ortho-dichlorobenzeue, melting at 302 to 304 C.

C H O N mol. weight, 575.59. Calculated: C, 77.20%; H, 4.38; N, 7.30%. Found: C, 77.44%; H, 4.44%; N, 7.41%.

55 of Z-phenylethylamine is refluxed for 1 hour, then cooled to room temperature, auctioned and the residue is washed with methanol, to yield 5.1 g. of a light-beige coloured powder which forms a turbid melt at 308 to 312 C.

o 0 CH: (1 E Q Q Q Q On crystallization from dichlorobenzene and clarification Small, pale-yellow needles from xylene, M.P. 354-356" C, with activated alumina, the compound of the formula 35- is obtained in the form of yellowish needles melting at 316 to 318 C.

36 73.63%; H, 4.73%; N, 10.10%. Found: C, 73.90%; H, 4.93%; N, 10.17%.

C l- 0 M: mol. weight, 588.64. Calculated: C, 77.53%; H, 4.79%; N, 9.52%. Found: C, 77.34; H, 4.90%; N, 9.44%.

The following benzoxazolyl-oxdiazolyl-stilbene compounds can be prepared in a similar manner:

Pale-yellow tinsel from trichlorobenziene, not melting below 350 C.

C H O N mol. weight, 590.61. Calculated: C, 75.24%; H, 4.66%; N, 9.48%. Found: C, 75.09%; H, 4.53%; N, 9.44%.

Yell'owish, small felted needles from ortho-dichlorobenzene, melting above 320 C. with decomposition.

C33H3503N4I mol. weight, Calculated: C, 76.48%; H, 6.08%; N, 9.39%. Found: C, 76.24%; H, 6.12; N, 9.29%.

Example A suspension of 51.5 g. of the methyl ester of the Formula 69 in 1200 ml. of ethyleneglycol monomethyl ether is heated to reflux, whereupon a thin suspension is ob Shiny, silvery tinsel from ortho-dichlorobenzene, melting at 320 C. with decomposition.

C l-1 0 1 1 mol. weight, 524.55. Calculated: C,

75.56%; H, 4.61%; N, 10.68%. Found: C, 75.35%; H, 4

tained. While stirring it well, 8 g. of caustic soda in 20 ml. of water are dropped in within 15 minutes, whereby a thick yellow suspension is obtained. The whole is refluxed for 5 another hour and then vigorously stirred into 3 liters of water and mixed with 80 ml. of concentrated hydro- Pale-yellow tinsel from ortho-dichlorobenzcne, melting at 305 C. with decomposition.

C l-[ 0.14g mol. weight, 542.57. Calculated: C,

73.05%; H, 4.83%; N, 10.33%. Found: c, 72.88%; H,

Small, yellow needles from ortho-dichlorobenzene, melting at 288 to 290 C.

chloric acid. The precipitate is suctioned off and the residue washed with water and sucked dry. The residue is then dissolved in dimethylformamide, an undissolved turbidity is filtered off and the whole is considerably concentrated and then allowed to cool. The crystalline precipi- CHr-CH tate is suctioned off, washed with a small amount of dimethylformamide and methanol and dried, to yield 46.8

C H O N mol. weight 554,58, Calculated: C, g. of a yellow powder which does not melt below 350 37 38 C. Recrystallization from dimethylformamide furnishes 8 g. of allylamine is refluxed for 2 hours, whereupon a the carboxylic acid of the formula turbid solution is obtained which is auctioned at room in the form of yellow flakes which do not melt below temperature and the residue is washed with methanol 350 C. and dried, to yield 4.1 g. of a light-yellow powder which C H O N mol. weight, 541.58. Calculated: C, melts at 300 C. with decomposition. Crystallization 75.40%; H, 5.03%; N, 7.76%. Found: C, 75.57%; H, 15 from chlorobenzene with the aid of active carbon fur- 5.22%; N, 8.03%. nishes the amide of the formula Example 11 A mixture of 44.5 g. of the carboxylic acid of the Formula 86, 350 ml. of dry chlorobenzene and 100 ml. of thionylchloride is stirred overnight at 100 C. whereupon the temperature is raised to 120 C. within one 3 hour. The batch is allowed to cool, finally cooled in an ice bath, suctioned at 10 C. and the residue is washed C II;

(I EDW- with dry chlorobenzene and hexane. After drying with exclusion of air there are obtained 36.5 g. of the acid chloride of the formula Small, light-yellow needles from chlorobenzene, melting at 300 to 303 C.

C H O N mol. weight, 652.80. Calculated: C,

in the form of a yellow powder which melts at 282 C.

77.27%; H, 6.79%; N, 8.58%. Found: C, 77.57%; H, with decomposition.

Small, yellow needles from ortho-dichlorobenzene, melt- 65 ing at 314 to 315 C.

C H QO N mol. weight, 644.74. Calculated: C, 78.24; H, 5.63; N, 8.69%. Found: C, 78.00%; H, 5.63%;

Example 12 A mixture of 4.2 g. of the carboxylic acid chloride of the Formula 87, 130 ml. of dry chlorobenzene and N, 8.91%.

/CHr-CH; o N

0 CH3 0 N- C CH=CH C M.

39. 40 Pale-yellow, small needles from chlorobenzene, melting C H O,N mol. weight; 631.73. Calculated: C, at 299 to 300 C. with decomposition. 77.95%; H, 5.27%; N, 6.65%. Found: C, 77.83%; H,

C ,,H O N mol. weight, 610.68. Calculated: C, 5.34%; N, 6.65%.

74.73%; H, 5.61%; N, 9.18%. Found: C, 74.65%; H, 5.61%; N, 9.28%. Yellow, granular powder from chlorobenzene, melting at 324 to 326 C.

C H O N mol. weight, 673.78. Calculated: C, 78.43%; H, 5.83%; N, 6.24%. Found: C, 78.03%; H,

Example 13 15 A mixture of 4.2 g. of the carboxylic acid chloride of the Formula 87, 2.5 g. of l-octadecanol, ml. of

O\ N o CH, CHaOCHgCHgOCH CHgO QCH= HQF CH 6... .l .l 4.... AIR

anhydrous chlorobenzene and 1 ml. of pyridine is refiuxed-for 4 hours, then allowed to cool, the precipitate 30 is suctioned off at room temperature and washed with a small amount of chlorobenzene and hexane. The lightbeige coloured residue is dissolved in 400 ml. of boiling dichlorobenzene, clarified with active carbon, considerably concentrated and allowed to crystallize. After drying there are obtained 3.8 g. of a pale-yellow, crystalline powder melting at 245 to 250 C. Recrystallization from chlorobenzene furnishes the compound of the formula Yellow, crystalline powder from chlorobenzene, melting at 247 to 250 C.

C H O N r mol. weight, 685.79. Calculated: C, 73.55%; H, 6.32%; N, 6.13%. Found: C, 73.55%; H, 6.22%; N, 6.27%.

Example 14 A polyester fabric (for example Dacron) is padded at room temperautre (about 20 C.) with an aqueous dispersion containing per litre 2 g. of the compound of the in the form of a light-yellow, granular powder melting at 250 to 255 C.

C52H6304N3: mOl. Weight, Calculated: C,

Formula 12 or 14 and 1 g. of an adduct from about 8 mols of ethylene oxide with 1 mol of para-tertiary octyl- 78.65%; H, 8.00%; N, 5.29%. Found: C, 78.73%; H, phenol, and then dried at about 100 C. The dry mate- 7.90%; N, 5.35%. rial is subjected to a heat treatment at 150 to 220 C.

The following benzoxazolyl-oxdiazolyl compounds can which, according to the temperature used, lasts from 2 be prepared in a similar manner: minutes to a few seconds. The material treated in this manner has a substantially whiter aspect than the un- Small, lemon coloured needles from chlorobenzene, melttreated material.

ing at 289 to 291 C.

C H O N mol. weight, 581.64. Calculated: C, 76.40%; H, 5.37%; N, 7.23%. Found: C, 76.18%; H, 5.61%; N, 7.42%.

Example 15 100 grams of a polyester granulate from polyter- CH; O N\ o Q (I Q e Q jj Qig with 0.05 g. of the stilbene derivative of the Formula Greenish yellow flakes from chlorobenzene, melting at 12, 13 or 14 and melted with stirring at 285 C. The spin- 272 to 273 C.

. 0 ephthalic acid ethyleneglycol ester are intimately mixed 

1. THE 4-OXAZOLY-4''-OXIDIAZOLYL STILBENE OF THE FORMULA 